Experimental verification of orbital engineering at the atomic scale: Charge transfer and symmetry breaking in nickelate heterostructures

Epitaxial strain, layer confinement, and inversion symmetry breaking have emerged as powerful new approaches to control the electronic and atomic-scale structural properties of complex metal oxides. Trivalent rare-earth (RE) nickelate RENiO3 heterostructures have been shown to be exemplars since the orbital occupancy, degeneracy, and, consequently, electronic/magnetic properties can be altered as a function of epitaxial strain, layer thickness, and superlattice structure. One recent example is the tricomponent LaTiO3-LaNiO3-LaAlO3 superlattice which exhibits charge transfer and orbital polarization as the result of its interfacial dipole electric field. A crucial step towards control of these parameters for future electronic and magnetic device applications is to develop an understanding of both the magnitude and range of the octahedral network's response towards interfacial strain and electric fields. An approach that provides atomic-scale resolution and sensitivity towards the local octahedral distortions and orbital occupancy is therefore required. Here, we employ atomic-resolution imaging coupled with electron spectroscopies and first-principles theory to examine the role of interfacial charge transfer and symmetry breaking in a tricomponent nickelate superlattice system. We find that nearly complete charge transfer occurs between the LaTiO3 and LaNiO3 layers, resulting in a mixed Ni2+/Ni3+ valence state. We further demonstrate that this charge transfer is highly localized with a range of about 1 unit cell within the LaNiO3 layers. We also show how Wannier-function-based electron counting provides a simple physical picture of the electron distribution that connects directly with formal valence charges. The results presented here provide important feedback to synthesis efforts aimed at stabilizing new electronic phases that are not accessible by conventional bulk or epitaxial film approaches.